Halogenated m-di-tert-butyl-benzenes



Patented Sept. 12, 1950 p NznNEs @arl-vE; JohnsonQSt; Louis, Micliv," and'sfihesterciEii I Adams, flighland lnd assigcmrs to Standamd Oil Company, Chicago, 111., a corporationnffi 7 Indiana;

No-Drawing: Application Maly 2W51947 1 Serial No. 750388rf I f invention relates m me chain (exo --;hale ogenat'edjm-di-tert-butylbenzenes and, to a proc- 4 essr for their production.

We. have discovered that. exo-halogenatedim di-tertl-butylbenzenes can be preparedreadily by theprocess whichwill hereinafter be. described:

and that they are surprisingly stable compounds which are of value inpreparing. various deriva.-.

tires" .In-order. to compare the "halogenatedni-di-w tert-butylbenzenes with, halogenated, p-div-tert-- butylbenzenes, we have prepared beta-tetrachloro derivatives from J mand p-ditert-butylbenzene; respectively. It shouldbemnderstood however, that. our inventionis concerned. with.

exo..-.halogenated m-di-tert-b.utylbenzenes,. par ticularly those having 1 to ohalogeni atoms, in,

elusive, the molecule. Wehaveefound that the m-tetrachloro.-dietertr-butylbenzenes:- can be: sulfionated and.,- neutralized.. with; caustic to; yield I a water-soluble sodium .sulionate derivativez havw However I I ing foaming and wetting properties. attempted sul-fonation-aofr-ptetrachlorc-dietertbutylbenzenes resulted in extensive decomposir-y.

tion, as. evidenced? by the generations of-ii-IGEI, and

nopsulfonic acid or sulfona-tee;cou1cL be--- isolated; other w cite-halogenated @edi-tBIit-blltfillbHZBDBS react.similarlya chain (exo) halogenated m-.c1-i-tert-butylben.-.= zenes containing 1=to-6::ha-1ogen atoms, inclusive. fim gg gg g fm Another objectds-to provide new compounds. An f ;3li \;ma

additional object is to provide a novel process for the preparation: of betashalogenated' m-di-tertbutylbenzenes, particularly, betaschlorinated mlitlis an obj ect of ourinvention toprey/tideF side.-

di-tert-butylbenzenes, such as tetrachloro-m-di- These and other ob'jects'will' tion was obtained from the fractionaljdistillartio Q E A-comparisoniofisoineiof tfie piiysica "p' W butylbenaene cansbeproduced in;firirlmgcod;

by, the l dialieylationzofl benzene witheisobutylenew irethe presence oft aluminum-1--chloride atarelaetively, high temperatures; for example-tempera;

The: medi-tert butylbenzene which is producedi. the alleylation reactionaoanrbeeseparateditom; the v isomeric: p-di-tert. -butylbenzenel rwhich a p pears. to sheaths only othergisomer inthe :reactiorra: mixture bntractionalidistillationl I ;:j We have; prepared medi-gtert-rhutylbenzene :by passing; 230 gramsyof isobutylene into avrapidl-ystirred mixture of 225'grams of benzene-(pra rie ousl-ysaturated at; room temperatures wi-tm dry HOD/. and l 15 g. of, anhudrous aluminumechloride over a. period or sshoursytheareactiontemperature beings... maintained between: about 130 .E; ands 1405; E The hydrocarbon QIOdUCt$nrWGHz frame. tionally distilled-under? reduaeri pressure. to -ob-.; tain ,jIEI'I-YiIi-HWt -bHtXIbSJiZEBQ; whieh :boils ata'ap proximatelyl'lfiefiifi. tuncorr hat4$mmaofmer -f cury pressure; l-Theeicllowingg produetr-clistribu.-.:-

operation:

compasses The process which we hay mployed iforthe preparation of halogenated m-di-tert-butylbenzenes comprises two principalstages namely;- the:

preparation of m-di-tert-butylbenzene and its halogenation.

m-Di-tert-butyZbenzene-{preparation Although the, literature.- reporitsaaanumber of preparations of' di-tert-butylben; nes'; no report has been made of thepreparationandtisolation of benzene with isobutylene' the resenee of alu minum chloride or other Fridel Ciraits catalysts at normal or moderate temperatures appears to yield almost exclusively the p-di-tert-butylbenzene. We have found, however, that m-di-terttert butyIbenZene ab'si'irHetYu-lti'aVmlet light in araiige'i lb wer-"tiian that of tiieipara is onieri 1 We rna'y emplov other metliods than the one described above for the preparation of m-di-tertbutylbenzene. For example, we may efiect the isomerization of p-di-tert-butylbenzene to the sufiicientl'y: high togiefiect isomerizatiori; 1e; g; terns. peratures-betwe'en about 130 F.-"an'd about 220FQ or even higher for a period of time sufficient to I,

efi'ect the desired amount of isomerization.

A solution was prepared of 23 g. of m-di-tertf butylbenzene and 150 cc. (204g) of carbon tetra chloride, to which were added 65.6 g. of sulfuryl' chloride and 1 g. of benzoyl peroxide. The resulting mixture was refluxed for 18 hours. The

tert-butylbenzenes has specifically been described,

chlorination of t 9714) utylb enz en el 1 itshould-be understood that our invention is not limited to chlorinated compounds or to compounds containing four halogen atoms in the molecule; Thus, it will be apparent that our inreaction product was washed with aqueous sodium hydroxide and dried by filtering through paper.

trogen on a steam bath for 3 hours; apale yellow visco oil remained as a residue from the "strip-1 ping operat on. The Weight Of'thTidllfil 1110 rinated"m ditert-butylbenzene was svls s, (96 of the theoretical yield) and its'inolecular'weight as" determined by; the Menziesmethod'us'ing benzene as the solvent "was 3'20. The molecular weight value obtainedico flpar's "well {with that for fa tetrachloro m di tert butylbenzne'. viz.

Carbon tetrachloride was then stripped. from the essentially water-free solution with n1 328; The chlorine content of the chlorinated m]- j di-tert-butylbenzenewas found to' be 41.9 per cem aswompared with the theoretical chlorine maneuver 43.3 per bent r 'r v tetrachloro-di-terta sample of the "tetrachloro m -di tert bu tyl or 0.5' N adiieousNaQHJ Only 2.75% of the chlorine'" present in "thecompound was removed. by"

this treatment. This is good evidence that the butyl groupsjattached to th'ebenzene ring were tertiary butyl' and not isobuty'l because itis known that chlorinaatoiris attached "to neop fi le b' diblYit.

It will be evident from the structure oTn'i -di vention extendslto other halogen compounds, such as'may be prepared by reacting m-di-tert-butylthe presence'of a peroxide catalyst. the use of benzoyl peroxide has been specifically described, other catalysts may be used, for example, lauroyl peroxide, dialkyl peroxides and the like. By suitably varying the ratio of sulfuryl chloride or other halo'genating' agent we may produce exo-halogenated m ditertbutylbenzenes containing lto 6 halogen.atoms, inclusive, in the molecule'filt should be understood that,although.

63.4 to 72.2 0. containing 42.8 percent of chlorine. Tetrachloro-p-di-tert-butylbenzene on treatment with 100% H2804 decomposed to yield HCl and a variety of other products.

Tetrachlorqem.dietert-butylbenzene did not decompose with 100% H2804; it was sul'fonated with 1 fuming H2504 to yield a sulfonic acid, -,This acid had a neutral equivalent of 455 (theory=410). The. high neutral equivalent is probably due to a trace of oil contaminating the product. The

sulfonic acid was converted to the sodium-salt reported in the literature.- 1 Thus, Baur'dissolved p-dietert-butylbenzene. in warm, concentrated sulfuric: acid to. produce a sulfonic acid-derivative (Ber.-27-,--1606 (189 1)). .1A di-tert-butylbenzene, probably thepara isomer, has also been reported whic we haveldescribed'a 'specific method for introj ducinga halogen atominto the tert-butyl side chains, we arenot limited to this method and may employ any other suitable method, e; g. free halogen in the presence of light or other catalyst i sde n h e 'e iq ra er thannuclear halogenation, The halogenatdim 'di-tertbutylbenzenes, parf, 1 ticularly V tetra-,chloi mm ditert biitylbenaene,if maybe employed as'a charging stock for the I preparation'of awideirariety of chemical derivatives, as for example by nuclear sulfonation, ni.; trationfhalogeriation. oxidation and the like; The relatively high stability of the carbon-chlo i, rine bondsin'the compounds ofthis invention" "permits modification of the em-an e r.

molecule] without therefrom: Y v.

Hvin tnus'ues ribed ourinvention, sha ts mixture? o' f isomeric 'b'eta-tetrac'hloro-ni-di tert-butylbehzenes, the chlorineatorns of which? are resistant to hydrolysis, such thatorily about 2.75 per cent of chlorineis removdirohis'aLid mixtureupon refluxing thereof with 0.5 N aqueous undesirable chlorine cleavage I CITED 1' 1 a The following references. are of recordin the fileof thispatentz. V V 1 5 UNITED STATES PATENTS FOREIGN PATENTS Number .Country D t 448,851 Great Britain June 10, 1936 mensmsesaisf Calcott et al., -J0ur. Am.- Chem. S004, vol. 61,

pages 1010-15 (1939). v Schmerlinget al., vol."67', page 1862 (1945'). r

JourxAm-x chem. $00.9 

